(1-amino-2-anthraquinonyl carbonylamino)-alkyl-1uaternary ammonium salts



United States Patent 3,076,821 v (l-AMINO-Z ANTHRAQUINONYL CAiRBONYLAMI- N0)-ALKYL-QUATERNARY AMMONIUMSALTS) Robert C. Hoare, Hamburg, N.Y., assign'or to Allied Chemical Corporation, New York, N.Y., "a corporation of New York No Drawing. Filed Nov. 8, 1960, Ser. No. 67,935

2 Claims. (Cl. 260-377) This invention relates to anthraquinone dyes, and more particularly to quaternary ammonium derivatives of amino-anthraquinones useful for dyeing polyacrylonitrile fibers including yarns and textiles containing such fibers.

Since the introduction into commerce of polymers and copolymers of acrylonitrile (hereinafter, for the sake of brevity, referred to as acrylic fibers), much research efffort has been devoted to the development of dyes for the dyeing of such fibers including yarns and textiles containing them alone or in admixture with :other fibers. Various quaternized amino-anthraquinone derivatives have been proposed for this purpose.

It is among the objects of the present invention to provide novel amino-anthraquinone dyestuffs for coloring acrylic fibers, including yarns and textiles containing such fibers alone or admixed with other fibers, which dyestuffs produce colors or shades which are both washand lightfast on acrylic fibers.

'Other objects and advantages of the dyestuffs or "the invention will be apparent from the following detailed description thereof.

The dyestuffs of this invention are cationic anthraquinone dyes having the formula:

aryl, are 'phenyl or naphthyl. The heterocyclic group, of which a and b may be parts, is a morpholind, piperidino, l

pyrrolidino-, or piperazino-radical.

The R substituent, when alkylamino, is r'nethylamiiio, t-butylamino, laurylamino, hydroxyethylamino, ethoxyethylamino, or hydroxyethoxypropylamino; desirably the alkyl group is lower alkyl containing, for example, from 1 to 4 carbon atoms.

The R, substituent, when arylamino, is anilino, anaphthylamino, tolylamino or 4-nitrophenylamino.

The R snbstituent, when cycloalkylamino, is methylcyclopentylamino, cyclohexylamino, methylcyclohex'ylamino or 'cyclophentylamino.

The cationic anthraquinone dyes of the present invenpo'ses.

avoided.

Patented Feb. 5, 1953 2 tioh are obtained bycondensing a l-amino-antbraquinone- 2 -carbonyl derivative corresponding to the desired dye which may be used instead of dimethyl sulfate include other lower dialkyl sulfates such as diethyl, dipropyl or dibutyl sulfate; lower alkyl halides such as methyl (ethyl or butyl iodide, methyl or ethyl chloride, propyl, butyl or hexyl bromide; aralkylhalides such as benzyl chloride; lower alkyl esters of organic sulfonic acids such as methyl, ethyl, propyl or butyl toluene'sulfonate's; or substituted alkyl halides such as ethylene or propylene chlorohydrin.

The quaternization reaction is performed in the presence of a solvent in which the dye base is soluble and which is relatively unreactive toward the quaternizing agent. Among the solvents that can be employed in this reaction are normal and tertiary butanol, monoand trichlor'ob'enzene, the Xylenes and benzene. The volume of the solvent is not critical. The solvent functions to provide a fluid reaction mass and the amounts can be varied considerably. The use of large quantities of solvent is ob- 'jectionable, however, because it is wasteful and expensive.

Inasmuch as the quaternization occurs at ambient or slightly elevated temperatures, it is preferred to carry out this step at moderate temperatures, i.e., at temperatures below C. Higher temperatures can be used, although in the presence of primary and secondary amino groups, reaction of the quaternizing agent with these substituents of the anthraquinone compound when present, should be The dyeing of acrylic fibers with cationic dyes involvis a simple ion exchange phenomenon in which the cation from the dyestuc replaces the anion contributed by the polyacryl'onitrile residue. Hence, it is evident that the dyestuif a'nion serves merely to assist in the solubilization of the dyestuff in the dye bath. Accordingly, other anions besides those included in the preceding list of quatternizing agents may be associated with the cationic dyestufi as long as the dyestuif is not thereby insolubilized in the dye bath. The anion can be varied considerably without materially affecting the application and coloration properties of the dyestuffs.

The dyeing of textiles or yarns containing acrylic fibers with the dyestuffs of this invention is carried out from aqueous dye baths, the pH of which is preferably slightly acid, i.e., about pH 4.5 or 5.5, although pH ranges of 3 to about 10 can be used. The most favorable conditions for any of the dyestuffs coming within the scope of the invention-pan readily be ascertained by a few trial experiments.

The following examples are given for illustrative pur- It will be understood that this invention is not limited to these examples. In the examples, all parts are on a weight basis and the temperatures are given in C.

3,07 3 EXAMPLE I A mixture of 50 parts of 1-arnino-anthraquinone-2- carbonyl chloride, 100 parts of N,N-dirnethylamino-l,3- propanediarnine and 200 parts of Water was heated to 95 After the addition of about 40 parts of secondary butyl alcohol, the mixture was heated under reflux for about 16 hours. The mixture was cooled to 30, filtered, washed with cold water and dried at 60.

The dried dye base was slurried in about 400 parts of with benzene and dried. The resulting dyestuff, N-benzyl- N-2(l-arninoanthraquinonyl-2-carbonylamino) ethylmorpholiniurn chloride having the formula chlorobenzene, and 26.6 parts of dimethyl sulfate were O added drop-wise. The mixture was agitated for about 16 H C- hours, filtered, washed with chlorobenzene and dried. 0 The dried product amounting to 44.4 parts and having the formula: r

H H: H: 0 NH H 2 /CH3 0 (EH:

--CNH(CHz):-l I CHa .CHiSOt dyed Orlon acrylic fiber from a boiling, weakly acid bath (pH 5) in orange shades of excellent fastness to washing and to light.

EXAMPLE II A mixture of 50 parts of l-arnino-anthraquinone-Z- carbonyl chloride, 100 parts of N-Z-aminoethyl-morpholine and 200 parts of Water was heated to 95". After the addition of 40 parts of secondary butyl alcohol, the mix ture was boiled under reflux conditions for 16 hours. The resultant mass was cooled to about 30, filtered and the filter cake after being washed with cold water was dried dyed Orlon in orange shades having excellent fastness properties.

EXAMPLES III to VIII, INCLUSIVE The 1-amino-authraquinone-Z-carbonyl derivatives and alkylene diamines given in Table I below were condensed and quaternized by substantially the same procedure described in Example I above, except that diethyl sulfate was employed as the quaternizing agent in Examples III,

V and VIII, and benzyl chloride was employed as the quaternizing agent in Example VI. Dimethyl sulfate, the

quaternizing agent used in Example I, was also used in 0 at about Examples tv and VII.

Table I Shade Produced by Example Anthraquinone Derivative Diamine Quutcrnized Derivative on Orion 0 NH; ll I /CH2 m o 0 c1 Nrn-ozrn-N Red.

CHI

0 N H2 II 02 IV C001 NHzCzH4-N Blue.

l O NHCH;

O NH: H I /CHa V COCI NHzCaHo-N Blue.

CH3 1 l O NH: [I ll /CHa VI -C 0 Cl NHzCaHr-N Blue.

CHa

i O NH Shade Produced by Example Anthraquinone Derivative Dlamine Quatemized,

Derivative on Orion N Hz ll /GH VII o 0 c1 H N-CiHp-N (Blue.

I O .NH CH2 0 NH: H (IJH: vnr -c0o1 HzN-CzHt-NO Blue.

i O NH The cationic anthraquinone dyestuir' of Example III has the formula:

The cationic anthraquinone dyestufl of Example IV has the formula:

The cationic anthi'aquinone dyestufl of Example V has the formula:

The cationic anthraquinone dyestufi? of Example VI has the formula:

The cationic anthraquinone dyestufi' of Example VII has the formula:

The cationic anthraquinone dyestufi of Example VIII has the formula:

in which n is an integer of from 2 to 4; a is selected 3,076,821 7 8 from the group consisting of alkyl of from 1 to 4 carbon 2. The compound of the formula: atoms, benzyl, hydroxyalkyl of from 1 to 4 carbon atoms, phenyl, naphthyl, and a, b and the quaternary ammo 0 NH! nium nitrogen form a heterocyclic radical selected from H 0 CH3 the group consisting of morpholino, piperidino, pyrroli- 5 fimsoh dino and piperazino; b is selected from the group consisting of alkyl of from 1 to 4 carbon atoms, benzyl, hydroxyalkyl of from 1 to 4 carbon atoms, phenyl and naphthyl; c is selected from the group consisting of 5 alkyl of from 1 to 4 carbon atoms, benzyl, hydroxy- 10 alkyl of from 1 to 4 carbon atoms, phenyl and naphthyl; A is an anion; and R is selected from the group 0011- References Cited in the file of this patent sisting of hydrogen, hydroxyl, alkylarnino of from 1 to 4 UNITED STATES PATENTS carbon atoms, anilino, naphthylamino, tolyarnino, 4-mitrophenylamino, methylcyclopentylamino, cyclohexyl- 15 1,871,321 Nawiasky et 16, 1932 amino, methylcyclohexylamino and cyclopentylamino, 2,924,609 Joyce Feb. 9, 1960 

1. A COMPOUNF OF THE FORMULA:
 2. THE COMPOUND OF THE FORMULA: 